Low temperature curable adhesive compositions

ABSTRACT

The present invention is concerned with curable adhesive compositions for anchoring elements in a structural body that exhibit low temperature versus standard temperature degree of cures that are at least 50% or higher. The compositions include, in a first component, a reactive resin, an acetoacetoxy functional monomer and a silane monomer. By using phthalate-free constituents in the formulation, a further 10% increase in strength and durability of the resins at standard temperatures may be realized after curing at low temperatures.

CLAIM OF PRIORITY

This application is a Continuation of patent application Ser. No.13/007,635, filed 16 Jan. 2011 (now U.S. Pat. No. 8,334,346, issued 18Dec. 2012). This application is herein incorporated fully by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to adhesive compositions suitable foranchoring or fixing elements in a base or structural body, and tomethods of anchoring. More specifically, the present invention isdirected towards adhesive compositions and methods that are especiallywell suited for curing such compositions at lower temperatures, withoutcompromising desirable characteristics such as strength and durability.

2. Discussion of the Related Art

It is well known that adhesive systems are useful for fixing oranchoring materials in or to rock, masonry, and concrete. Such systemstypically involve the use of synthetic resins and monomers that aremaintained separately from a hardening or curing agent until they arecombined at or near the point of fastening. A variety of additional andoften optional adjuvants may also be used with adhesive systems.

By way of example, U.S. Pat. No. 5,157,072 to Hense, et al., teachesethylenically unsaturated, substituted cycloaliphatic compounds asmonomers and resins for minimizing shrinkage of the adhesive when usedfor anchoring bolts in bore holes. However, Hense, et al., is silent onlow shrinkage stress. U.S. Pat. No. 5,288,767 to Cramer, et al., teachesa methacrylate monomer in the first component together with diluentmonomers. One of the stated goals of this patent is to eliminate styreneas a comonomer, but Cramer, et al., is silent on the subject oflow-temperature curing. U.S. Pat. No. 6,037,408 to Weber, et al., issimilar to the Cramer '767 patent, but it requires the use of very highlevels of monomer and is silent on the affects of low temperature cure.Variously, U.S. Pat. No. 6,583,259, Weber, et al., is concerned withadhesives to bond to wet bore holes; U.S. Pat. No. 7,544,739, to Liu, etal. teaches a composition for use under conditions of elevatedtemperatures; and U.S. Pat. No. 5,077,324 to Kistner, et al., isconcerned with extending the shelf life the formulation prior to use.Neither any of the foregoing, nor a great many other references aredirected towards adhesive compositions that are suitable for curing atlow temperatures.

It is often the case that adhesives must be applied to anchoringelements in concrete and masonry under adverse weather conditionsinvolving low temperatures and/or excess moisture. Unfortunately, it isnot until the arrival of warmer weather at some later point in time thatweakness or failure of the anchoring elements are observed. The effectsof warming the substrate have been largely ignored in the past. Often,products that are developed for cold environments make the assumptionthat the substrate will not warm appreciably. Another tactic that hasoften been employed is to produce multiple variations of a product whereseveral closely related compositions are developed, each associated witha specific temperature range. Under new protocols, however, the costsfor testing can be prohibitive for a product line with multipleadhesives.

SUMMARY OF THE INVENTION

In light of the foregoing, it is desirable to provide an adhesivecomposition that not only can be cured at low temperatures, but thatalso exhibits good strength and structural integrity over a wide rangeof temperature conditions. Moreover, another disadvantage of manyadhesive compositions that are currently commercially available is thatthey contain or include phthalates. Phthalates, or phthalate esters, areoften used in adhesive formulations as phlegmatizing agents to preventthe rapid and explosive reaction of certain curing agents when they arephysically disturbed. Over concerns related to health reasons, however,phthalates are being phased out of many products in the United States,Canada, Europe and elsewhere in the world. Accordingly, it is desirableto provide an adhesive composition that does not include phthalates yetdoes not compromise safety.

The present invention provides an adhesive composition for anchoringmaterials in or to concrete or masonry that comprises from about 20% to80% by weight of the entire composition of a reactive resinmonomer/acetoacetoxy monomer/silane monomer solution; and a curingagent. In one aspect, the present invention provides a composition foranchoring materials in or to concrete or masonry that is made by mixinga first composition and a second composition. The first compositioncomprises from about 20% to 80% by weight of the entire composition of areactive resin/acetoacetoxy monomer/silane monomer solution; in additionto an accelerant; inhibitor; and filler. The second compositioncomprises a curing agent; diluents as required to provide aphlegmatizing agent or flow; and filler.

According to another aspect, the present invention provides aphthalate-free composition for anchoring materials in or to concrete ormasonry that is made by mixing a first composition and a secondcomposition. The first composition comprises from about 20% to 80% byweight of the entire composition of a phthalate-free methacrylatemonomer/acetoacetoxy monomer/silane monomer solution; in addition to anaccelerant; an inhibitor; a filler and optional adjuncts. The secondcomposition comprises a free radical initiator; phthalate-free diluentsas required to provide a phlegmatizing agent or flow; and optionaladjuncts.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides an adhesive composition for anchoringmaterials in or to concrete or masonry. The materials to be anchored inor to concrete or masonry include, but are not limited to: metallicobjects such as steel rods and steel bolts; ceramics; other concrete ormasonry members; plastics; glasses; and woods.

As indicated above, one of the motivating factors for the presentinvention was to develop an adhesive composition that cured at lowtemperatures without compromising strength of the adhesive. In thecourse of developing such a composition, it was also recognized that itmight also be possible to impart other desirable features to theadhesive composition. Thus, it was postulated that the inclusion of asilane group, for example, might help promote adhesion of thecomposition to a cementitious substrate in wet or humid conditions. Inaddition, it was felt that an acetoacetoxy functional group might helppromote adhesion of the composition to the insert, the substrate, orboth. Under most conditions, these two monomers do not appear tosignificantly improve performance of an anchoring adhesive.Surprisingly, however, it was found that the presence of both anacetoacetoxy moiety and a silane moiety can provide a synergistic effectwhen curing takes place at low temperatures. Use of these monomers hasunexpectedly resulted in demonstrably better curing at low temperatures.For instance, when acetoacetoxyethyl methacrylate and methacryloxypropyltrimethoxysilane (MPTMS) are used together in a first adhesivecomposition, a 20% improvement in mechanical strength has been observedwhen the adhesive was cured at low temperatures and then warmed tostandard temperature.

Quite surprisingly, during the development of the inventive adhesivecompositions described herein, it has also been discovered that thesynergistic effect obtained upon the combination of silane andacetoacetoxy moieties is unexpectedly enhanced by the presence of aphthalate-free free radical initiator. Remarkably, the inventiveadhesive compositions described herein have been shown to be curable atlow temperatures, without any compromise as to strength, durability orstructural integrity whether at low, moderate or elevated temperatures.In other words, the inventive silane-containing, andacetoacetoxy-containing compositions described herein, which canadditionally be prepared phthalate-free, may be cured at lowtemperatures and yet retain the ability to perform at least as wellas—if not better than—commercially available adhesive compositions,whether at low, moderate or elevated temperatures. The use ofphthalate-free components in the inventive formulations can result in anapproximately 10% increase in strength and durability characteristicsfollowing cure at low temperatures.

Reactive Resin

In discussing resins and monomers herein, it is to be understood thatthese terms may be used interchangeably. The molecules which are oftenreferred to as resins are in reality high molecular weight monomers,from a chemistry standpoint. However, the terms resin and monomer areoften used interchangeably in the adhesives trade and thus the terms areused without chemical distinction herein. No limitation(s) are intendedor implied in the inventive adhesive compositions based on suchterminology.

The inventive adhesive compositions comprise, in a first component orfirst composition, at least one synthetic resin or polymerizable monomerselected from among: acrylate monomers; allylic resins; bismaleimideresins; epoxy acrylate resins; epoxy methacrylate resins; methacrylatemonomers; phenolic-based acrylates; phenolic-based methacrylates;unsaturated polyester resins; urethane acrylate resins; urethanemethacrylate resins; and vinyl ester resins. In one embodiment, one ofthe synthetic resins is preferably an alkoxylated bisphenol or a novolaccompound having one or more functional acrylate or methacrylate groups.A novolac—also spelled novolak—is a phenol-aldehyde condensationprepolymer obtained by condensing phenolic monomers with astoichiometric deficiency of aldehydes.

In one aspect, an adhesive composition of the present invention includesat least one polymerizable monomer that contains or includes at leastone functional group selected from among: acrylates; methacrylates; aswell as combinations thereof; in combination with a phenolic selectedfrom among; bisphenol A; bisphenol F; bisphenol S; novolac monomers; andcombinations thereof. In a preferred aspect of the invention, thereactive resin includes an alkoxy group. In a more preferred aspect ofthe invention, the alkoxy group(s) is positioned in the reactive resinbetween the phenolic and the acrylate or methacrylate group(s).Especially preferred for use with the present invention are alkoxylatedmethacrylates and alkoxylated dimethacrylates, with ethoxylatedbisphenol A dimethacrylate being particularly preferred.

Ethoxylated bisphenol A dimethacrylate resins with no more than 4 moleethoxylation are particularly suitable for use in the first compositionof the inventive adhesive formulations of the present invention. Degreesof condensation of ethylene oxide groups from about 1.0 mole to about4.0 mole are preferred, with an average degree of condensation of about2.0 mole to above 4.0 mole being more preferred. This resin isdifunctional and has relatively few ethoxylate groups, thus it has goodcrosslink density, which results in high mechanical strength. Thismonomer also has a high glass transition temperature, T_(g), whichallows for higher end use temperatures of the adhesive. It also has avery high molecular weight and subsequently exhibits very low shrinkagestress. Without being bound by theory, the ethoxylate groups arebelieved to help promote adhesion to cementitious substrates.

Diluent Monomer

Diluent monomers, also called reactive diluents, are often used inadhesive compositions to bring the viscosity of a reaction mixture intoa desirable range. Such diluents are also used to incorporatefunctionality to improve the adhesion of these compositions to theinsert, the substrate, or both. Both multifunctional and monofunctionaldiluents may be used with the low temperature curable compositions ofthe present invention. Multifunctional diluents can be used to impartgreater crosslink density which can improve chemical resistance,moisture tolerance and performance at higher use temperatures.Accordingly, either liquid or solid reactive organic diluents may beused with the reactive resins described herein to provide viscositycontrol, impart functionality, and/or increase the cross-linking densityof the reaction mixture; as such, use of diluent monomers is onlyrequired for reaction mixtures in which the afore mentioned propertiesmust be altered. If a diluent monomer is used it is therefore desirablethat the diluent monomer contain at least one functional group that isreactive with the polymerizable monomer described above. High molecularweight is also desirable in a diluent monomer; high molecular weightminimizes shrinkage stress and imparts low volatility. Reactive diluentsare optional for the present invention; however, those reactive diluentssuitable for use with the adhesive compositions of the present inventioninclude ethylenically unsaturated monomers. Among ethylenicallyunsaturated monomer diluents that can be used with the presentinvention, it is preferred that the reactive organic diluent include atleast one monofunctional monomer to lower viscosity and at least onemulti-functional monomer to increase crosslink density. As with thereactive resin, polar groups such as alkoxylates; carbonyls; etherlinkages; ester linkages; hydroxyls; amines; and amides are believed toimprove adhesion to the substrate.

As indicated above, monofunctional monomers may also be used with theinventive adhesive formulations. Suitable monofunctional monomers foruse with the present invention include, but are not limited to: methylmethacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butylmethacrylate, steryl methacrylate, 2-phenoxyethyl methacrylate,tetrahydrofurfuryl methacrylate, glycidyl methacrylate, isobornylmethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate,hydroxybutyl methacrylate, benzyl methacrylate, dicyclopentylmethacrylate, tert-butyl acrylate, steryl acrylate, 2-phenoxyethylacrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, hydroxybutylmethacrylate, benzyl acrylate, dicyclopentyl acrylate, and the like, aswell as combinations thereof.

Multifunctional monomers that are suitable for use with the presentinvention include, but are not limited to: ethylene glycoldimethacrylate, diethlyene glycol dimethacrylate, triethylene glycoldimethacrylate, dipropylene glycol dimethacrylate, 1,3-butylene glycoldimethacrylate, l,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol dimethacrylate, cyclohexane dimethanoldimethacrylate, dicyclopentyl dimethacrylate, glyceryl trimethacrylate,trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate,ethylene glycol diacrylate, diethlyene glycol diacrylate, triethyleneglycol diacrylate, dipropylene glycol diacrylate, 1,3-butylene glycoldiacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate,dicyclopentyl diacrylate, glyceryl triacrylate, trimethyloipropanetriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol pentaacrylate,tris(2-hydroxy ethyl)isocyanuratetriacrylate, alkoxylated variations of the foregoing monomers, and thelike, as well as any combinations thereof. Additionally metallicacrylates and methacrylates can be use to increase crosslink densitythese include, but are not limited to acrylates and methacrylates ofzinc, magnesium and calcium.

Other monomers, such as vinyl, allylic and acrylamide monomers may alsobe used. Examples of these monomers which can be used with the presentinvention include, but are not limited to: styrene; vinyl toluene;methyl styrene; divinyl benzene; allyl methacrylate; allyl cinnimate;allyl glycidyl ether; acrylamide; methacrylamide; N-methylol acrylamide;N-methylol methacrylamide; as well as combinations thereof. The use ofvinyl, allylic, and acrylamide monomers with the inventive compositionsdescribed herein is not preferred, however, due to possible healthconcerns.

Preferred diluent monomers for the present invention include:hydroxypropyl methacrylate, isobornyl methacrylate, tert-butylmethacrylate, methyl methacrylate, tetrahydrofurfuryl methacrylate,benzyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropanetrimethacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, andtrimethylolpropane triacrylate. Tetrahydrofurfuryl methacrylate andtrimethylolpropane trimethacrylate are particularly preferred.

Acetoacetoxy Functional Monomer

As indicated above, the use of an acetoacetoxy functional monomer hassurprisingly been found to provide an unexpected, beneficial synergisticeffect with respect to curing at low temperature when used in thepresence of a monomer that contains a cross-linkable silane group. Inaddition to the main monomer described above, the adhesive compositionsof the present invention therefore also comprise an ethylenicallyunsaturated monomer that contains at least one cross-linkableacetoacetoxy functional group. Acetoacetoxy functionality can beincorporated into the polymer matrix in the inventive adhesives usingacetoacetoxy alkyl acrylates such as, but not limited to:acetoacetoxyethyl acrylate; acetoacetoxyethyl methacrylate; diacetoneacrylamide; acetoacetoxy vinyl ether; as well as combinations of any ofthe foregoing. A preferred reactive monomer diluent is acetoacetoxyethylmethacrylate, often abbreviated AAEM.

Silane Monomer

As indicated above, the adhesive compositions of the present inventionalso comprise an ethylenically unsaturated monomer that contains atleast one cross-linkable silane group. Cross-linkable silane groups thatare preferred for use with the inventive compositions comprisehydrolizable alkoxy groups. Examples of hydrolizable alkoxy groups thatare suitable for use with the present invention may be selected fromamong: hydroxy group; halogen atom; alkoxy group; and acyloxy group; aswell as combinations of any of the foregoing. Silane monomers havingalkoxy groups are preferred.

Examples of monomers having both a point of polymerizable unsaturationand a cross-linkable silicon group include: methacryloxypropylpolyalkoxy silanes such as methacryloxypropyl trimethoxysilane,methacryloxypropylmethyl dimethoxy silane and methacryloxypropyltriethoxy silane; acryloxypropyl polyalkyloxy silanes such asacryloxypropyl trimethoxy silane, acryloxypropylmethyl dimethoxy silane,and acryloxypropyl triethoxy silane; vinylalkyl polyalkyloxy silanessuch as vinyl trimethoxysilane, vinylmethyl dimethoxy silane and vinyltriethoxy silane; as well as combinations of any of the foregoing.

Curing Agent

Curing agents in the present invention are free-radical initiators usedwith adhesive compositions in order to initiate polymerization andprovide cross-linking of the adhesive. Free radical initiators that aresuitable for use with the present invention may be selected from among:peroxides; peracids; peresters; and peroxymaleates; as well ascombinations of any of the foregoing. In addition, the adhesivecompositions may also be cured by using physical curing techniques suchas, but not limited to: radiant energy; thermal energy; as well ascombinations thereof. Combinations of free radical initiators withphysical techniques may also be appropriate for use with the lowtemperature adhesive compositions provided herein. Examples of peroxidesthat are suitable for use with the present invention include, but arenot limited to: cumene hydroperoxide; cyclohexanone peroxide; diacylperoxide; benzoyl peroxide; dibenzoyl peroxide; diisopropylbenzenedihydroperoxide; hydroperoxide; lauryl peroxide; methyl ethyl ketoneperoxide; p-butyl hydroperoxide; and mixtures thereof. Dibenzoylperoxides are preferred peroxides.

Non-reactive diluents are often used with dibenzoyl peroxide to addstability to the product. Examples of non-reactive diluents used tostabilize dibenzoyl peroxide include, but are not limited to: di-n-butylphthalate; diisobutyl phthalate; dicyclohexyl phthalate;butylbeuzylphthalate; trialkylphosphates; triarylphosphates;alkylarylphosphates; alkyl ethers of mono and diethylene glycols, alkylethers of mono and dipropylene glycols; benzoates of mono and diethyleneglycols; benzoates of mono and dipropylene glycols; water; and the like.Additionally, non-reactive diluents such as ethylene glycol, propyleneglycol, glycerol, urea and the like are often used to lower the freezingpoint of benzoyl peroxide mixtures. In one aspect of the presentinvention phthalate-free dibenzoyl peroxide mixtures are preferred.

Accelerants

Accelerants may be used with the adhesive compositions of the presentinvention. As will be understood by those skilled in the relevant art,the accelerant(s) that is appropriate for use with the low temperatureadhesive compositions of the present invention will vary, depending uponselection of a free radical initiator. Accelerants that are suitable forcuring via free radical mechanism include, but are not limited toorganic compounds selected from among: thioamides such as thiourea, acylthiourea, tetramethyl thiourea, diethylthiourea, dibutyl thiourea,ethylene thiourea, trimethyl thiourea, triphenyl thiourea and trioylthiourea; mercaptobenzimidazol; tertiary amines such as N,N-dialkyltoluidines, where the alkyl group is selected from among methyl, ethyl,hydroxyethyl, hydroxyl propyl, isopropyl and mixtures thereof; trialkylamines, where alkyl is selected from among ethyl, propyl, and ethyldiethanol; N,N-dialkylanilines such as N,N-dimethylaniline andN,N-diethylaniline; 4,4-bis(dimethylamino) diphenylmethane; and mixturesthereof.

Inorganic materials as well as organic salts may also be used asaccelerants with the present invention. Examples of inorganics andorganic salts that are suitable for use with the inventive adhesivesinclude, but are not limited to: magnesium; tin; and certain salts suchas cobalt naphthenate. It is also possible to use more than oneaccelerant with the inventive adhesives. Accordingly, in one aspect, theinventive adhesive compositions may include an organic compound, aninorganic, an organic salt as well as combinations of any of theforegoing.

In the course of the inventive work described herein, it has also beenfound that formulations including dibenzoyl peroxide also preferablycontain an accelerating agent in the first component with the resin andmonomers. Accelerators suitable for use herein may be selected fromamong: N,N-diisopropanol-p-toluidine, N,N-dihydroxyethyl-p-toluidine;N,N-methylhydroxyethyl-p-toluidine; and mixtures of the foregoing.

Fillers

Adhesive compositions that are used for anchoring members often containfillers to both impart strength and reduce cost. As will be appreciatedby those knowledgeable in the relevant art, fillers can also be used tocontrol viscosity. Fillers that are appropriate for use with the presentinvention include, but are not limited to: silica fume; quartz sand;finely ground quartz; a metal oxide such as magnesium oxide, iron oxide,aluminum oxide, and calcium oxide; clinker; calcium carbonate; metalshavings or particles; barium sulfate; aluminum trihydrate;wollastonite; kaolin clay; mica; feldspar; nepheline syenite; glassbeads; corundum; talc; chalk; ceramic microspheres; and cement; inaddition to combinations of any of the foregoing. In one aspect, eitherthe first composition or the second composition comprising the inventiveadhesives contains at least one filler, which may comprise the same ordifferent fillers. In another aspect, both the first composition and thesecond composition contain fillers. In yet another aspect of theinvention, the first component preferably contains at least one fillerthat is reactive with water, examples of which include cement and metaloxides. Cement is often a preferred filler, as it ties up water in theadhesive system and allows for better performance when an anchor isexposed to elevated temperatures after cure. As will be understood bythose skilled in the relevant art, fillers may be mixed into the first,monomer component and/or the second, curing agent component of theinventive adhesives.

Inhibitors

Inhibitors are required to prevent polymerization of the monomers andresins of the first component during storage. Inhibitors are present inreactive resins and monomers as they are received from manufacturers;however, additional inhibitor is often required to improve shelf life ofthe final product or to counteract the presence of the accelerator.Polymerization inhibitors appropriate for the present invention include,but are not limited to: methyl hydroquinone, hydroquinone, catechol,hydroquinone monomethyl ether, mono-tert-butyl hydroquinone,di-tert-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone,p-benzoquinone, trimethyl hydroquinone, napthaquinone, di-tert-butylmethylphenol, and combinations of any of the foregoing.

Thixotropic Agents

Thixotropic agents are often used in adhesive compositions to reduce thetendency of the liquid resin to flow or drain from vertical surfaces.Thixotropic agents that are suitable for use with adhesive compositionsof the present invention include, but are not limited to: fumed silica,organosilicas, clays and silicic acid. Commercially available fumedsilicas that are particularly suitable for use with the presentinvention are sold under such trademarks as Aerosil® available fromEvonik Industries, and Cab-o-Sil® available from Cabot Corp.

Adjuncts

It is recognized that other components or adjuvants known to thoseskilled in the art may also optionally be included in the inventiveadhesive compositions. Such components may include, but are not limitedto: antifoaming agents; catalysts; coupling agents; non-reactivediluents; dyes; fillers; fungicides; impact modifiers; odor maskants;pigments; solvents; stabilizers; surfactants; wetting agents; as well ascombinations of any of the foregoing.

Formulations

A number of different formulations that included varying amounts of theabove active and optional ingredients were prepared and evaluated forcuring at low and medium temperatures, and testing at low, medium andhigh temperatures. The term “low temperature” as used herein isunderstood to indicate temperatures on the order of approximately −10°C.±3° C. (14° F.±4° F.). The term “medium temperature,” “ambienttemperature”, “standard temperature” or “average temperature” as usedherein is understood to refer to room temperature or temperatures ofapproximately 23° C.±3° C. (72° F.±4° F.). The term “high” or “elevatedtemperatures” as used herein is understood to indicate temperatures onthe order of approximately 82° C.±3° C. (180° F.±4° F.). Thus, a varietyof different reactive main monomers were used in combinations withacetoacetoxy-containing monomers, both with and without monomers thatcontained silane groups.

Phthalate-Free Compositions

As indicated above, formulations that comprised a reactive resin towhich an acetoacetoxy-silane monomer combination was added were found toexhibit remarkably good strength and durability characteristics at roommedium temperatures following curing at low temperatures. In manyinstances, the performance of these inventive adhesive compositionsshowed nearly a two-fold improvement over other formulations that didnot include the acetoacetoxy-silane monomer combination. Even moreunexpectedly, however, a further improvement in performancecharacteristics was observed when adhesive compositions were formulatedwithout the presence of any phthalate moieties. Phthalate-free adhesivecompositions of the present invention have surprisingly been found to beespecially well-suited for curing at low temperatures. On average, theremoval of phthalates from the inventive reactiveresin/acetoacetoxy/silane monomer combination resulted in a 10%improvement in performance over adhesive compositions in whichphthalates were included.

Phthalates are typically introduced into adhesive compositions with thefree radical initiators that are used. According to one aspect of thepresent invention, therefore, noticeable improvements in adhesiveperformance can be observed in formulations at standard temperaturesfollowing cure at low temperatures when free radical initiators are usedin the inventive adhesives that are phthalate-free. Examples ofphthalate-free free-radical initiators that are suitable for use withthe present inventive include dibenzoyl peroxides. Phthalate-freedibenzoyl peroxides are commercially available under a variety of brandnames such as, but not limited to, the Perkadox® series of free radicalinitiators available from Akzo Nobel and Luperox® series of free radicalinitiators from Elf Atochem.

EXAMPLES

A number of adhesive compositions were prepared in accordance with theteaching of the present invention for use in comparison to commerciallyavailable adhesive compositions. Performance characteristics wereevaluated after cure at standard room temperature of 23±4° C. (73±8° F.)and at lower temperatures of −10° C. (14° F.) to mimic curing in coldconditions. Test members were prepared as follows. A channel or borehole was created in a formed or smooth steel-troweled face of a Portlandcement-based concrete test member of compressive strength in the rangeof 25.3 to 28.0 MPa (3,666 to 4,059 psi). The bore hole was made using arotary-hammer drill with a 17.5 mm ( 11/16 inch) diameter carbide bitmeeting the requirements of American National Standards InstituteBulletin 212.15 (ANSI B212.15, available in the United States from theCemented Carbide Producers' Association). The bore hole was drilled to adepth of 79.4 mm (3.125 inch) embedment, perpendicular to the testsurface. The channel chamber was then cleaned by blowing compressed airat 0.59 MPa (85 psi) into the hole for four seconds, followed bybrushing the bore hole for four complete strokes using a nylon brush ofgreater diameter than the bore hole, followed by blowing compressed airat 0.59 MPa (85 psi) into the hole a second time, also for four seconds.The anchoring adhesive to be tested was then injected into the bore holein such a manner as to ensure that the bore hole was evenly filled fromthe bottom of the chamber to a point approximately two-thirds full. A15.9 mm (⅝ inch) diameter threaded metal rod was then inserted into theadhesive with a slight twisting motion and the adhesive and insert wereallowed to cure undisturbed for one hour. After one hour, a load wasplaced on the metal rod anchors in tension until the point of failure inaccordance with test methods in ASTM E488 as modified by ICC-ESAcceptance Criteria AC308. Tensile testing was performed using anin-house confined or restrained tension testing rig using a 13.6 kg (30ton) hydraulic ram and a 22.7 kg (50 ton) load cell, in compliance withASTM E488 as modified by ICC-ES Acceptance Criteria AC308. The confinedtest setup was used to maximize strain on the adhesive while minimizingthe risk of concrete failure.

For the evaluation of inventive formulations after cure at lowertemperature, another series of smooth-faced, steel-troweled Portlandcement-based concrete test members were prepared in a manner identicalto the procedure outlined immediately above. The prepared test memberswere then placed into a controlled temperature chamber maintained at−10° C. (14° F.) and allowed to come to temperature equilibrium over thecourse of several days. The anchoring adhesive was then injected intothe bore hole in the temperature controlled chamber, filling the drilledcavity from the bottom of the bore hole to a point approximatelytwo-thirds full. A 15.9 mm (0.625 inch) diameter threaded metal rod wasthen inserted into the adhesive with a slight twisting motion and theadhesive and insert were left undisturbed and permitted to cure at −10°C. (14° F.) for twenty-four hours. At the end of that period, the testmember was removed from the controlled temperature chamber and allowedto come to room temperature of approximately 23±4° C. (73±8° F.). Theanchors were again loaded in tension until the point of failure inaccordance with test methods in ASTM E488 as modified by ICC-ESAcceptance Criteria AC308, as indicated above. Tensile testing wasperformed using a confined or restrained tension test. The confined testsetup was used to maximize strain on the adhesive while minimizing therisk of concrete failure.

Tables 1, 2 and 3 below contain the results of tensile tests performedon a variety of adhesive compositions that were cured at differenttemperatures in the manner described above. The compositions that wereevaluated include commercially-available adhesive products as indicatedin Table 1. Tables 2 and 3 contain a summary of a number of differentformulations that were evaluated during the development of the inventivelow-temperature cure compositions described herein.

Specifically and with reference to Table 1, the commercially availableadhesives that were evaluated include: 1) HY 150 Max, manufactured byHilti Aktiengesellschaft of Schaan, Liechtenstein, available in theUnited States online and through various distributors; 2) AC100+ Gold™,available from Powers Fasteners, Inc., of Brewster, N.Y.; 3) FIS VW fromFischerwerke GmbH and Co. KG of Waldachtal, Deutschland, not availablein the United States; and 4) Sikadur® AnchorFix-1, from Sika AG of Baar,Switzerland, and available through various distributors in the UnitedStates. Both HY 150 Max and AC100+ Gold™ have approvals in the UnitedStates for installations under low temperature cure conditions. HY 150Max, FIS VW and AnchorFix-1 have approvals in Europe for installationsunder low temperature cure conditions.

TABLE 1 Test Results for Competitive Products Bond Strength After Cure(MPa) Company Hilti Powers Fischer Sika Product HY150 Max AC100+ GoldFIS VW Anchorfix-1 Cure at 23° C., 16.69 9.09 14.77 12.12 Test at 82° C.Cure at 23° C., 21.95 16.32 18.62 15.44 Test at 23° C. Cure at −10° C.,14.52 9.40 10.69 9.58 Test at 23° C. Cure at −10° C., 19.71 NE^(a)NE^(a) 12.17 Test at −10° C. Low Temperature vs. Standard TemperatureDegree of Cure^(b) 66.2% 57.6% 57.4% 60.3% Phthalates present? Yes YesYes Yes Notes to Table 1 ^(a)NE—Not Evaluated ^(b)This calculated valueis the ratio of the strength at 23° C. after cure at −10° C. compared tothe strength at 23° C. after cure at 23° C., expressed in percent.

Table 2 contains a summary of representative formulations that weretested over a range of different concentrations combinations. TheExamples in Table 2 are comparable in strength to the competitiveproducts shown in Table 1.

TABLE 2 Formulations and Test Results of Example Compositions Example 12 3 4 5 6 First Component Reactive Resin 22.4% 17.5% 22.3% 17.1% 17.1%17.0% Diluent monomer 15.2% 25.0% 15.1% 20.8% 20.8% 20.2% Filler 60.2%54.3% 59.8% 59.3% 59.2% 59.7% Inhibitor <0.1% <0.1% <0.1% <0.1% <0.1%<0.1% Accelerator 0.2% 0.3% 0.8% 0.3% 0.4% 0.6% Miscellaneous^(a) 2.0%2.9% 2.0% 2.5% 2.5% 2.5% Second Component Free radical initiator 11.9%13.0% 14.8% 14.6% 21.3% 14.5% Nonreactive diluent 36.9% 40.2% 33.0%35.6% 35.7% 35.6% Filler 48.0% 43.5% 48.9% 45.6% 45.9% 45.3%Miscellaneous^(a) 3.2% 3.3% 3.3% 4.2% 5.1% 4.6% Bond Strength After Cure(MPa) Cure at 23° C., Test at 82° C. 13.04 10.31 10.99 11.05 9.57 12.88Cure at 23° C., Test at 23° C. 15.78 10.46 16.31 15.03 15.32 21.83 Cureat −10° C., Test at 23° C. 7.99 4.96 11.52 10.26 9.21 13.50 LowTemperature vs. Standard Temperature Degree of Cure^(b) 50.6% 47.4%70.7% 68.3% 60.1% 61.9% Phthalates present? Yes Yes Yes Yes Yes YesNotes to Table 2 ^(a)Selected from amoung pigments;thixotropes;dyes andcolorants; etc. ^(b)This value, calculated for the entries in the tablefrom their bond strengths, is the ratio of teh strength at 23° C. aftercure at −10° C. compared to the strength at 23° C. after cure at 23° C.expressed in percent.

Following the initial discovery that acetoacetoxy-silane monomersimparted discernable low-temperature cure improvements to the mainreactive resins, a series of experiments were conducted usingphthalate-free initiators. As these latter adhesive formulationsexhibited even more remarkable strength characteristics at mediumtemperatures following low temperature cure, a number of experimentswere conducted in order to evaluate alternate adhesive compositions. Theresults of these studies are summarized in Table 3 below. Examples Athrough C of Table 3 represent a preferred aspect of the presentinvention, in that they provide phthalate-free compositions well-suitedfor low temperature core. In examples A and B the phthalate-free radicalinitiator used was Perkadox® L-40 RPS; and in example C the free radicalinitiator used was Perkadox® BTW50. Examples D through G represent analternate aspect of the present invention in which the adhesivecomposition is not phthalate-free. Perkadox® 40e was used as the freeradical initiator in examples D through G.

TABLE 3 Formulations anti Test R..e.stifts for Sm-ripk Compositionti:Example A B C D E F G First Component Reactive Resin 18.0% 18.0% 18.0%18.0% 16.8% 16.8% 13.6% Acetoacetoxy monomer 1.7% 1.7% 1.7% 1.7% 3.2% 0%0% Silane monomer 0.5% 0.5% 0.5% 0.5% 0.9% 0.9% 1.0% Diluent monomer19.4% 19.4% 19.4% 19.4% 16.8% 20.0% 23.3% Filler 57.3% 57.3% 57.3% 57.3%59.2% 59.2% 59.3% Inhibitor <0.1% <0.1% <0.1% <0.1% <0.1% <0.1% <0.1%Accelerator 0.9% 0.9% 0.9% 0.9% 0.6% 0.6% 0.5% Miscellaneous^(a) 2.4%2.4% 2.4% 2.4% 2.5% 2.5% 2.3% Second Component Free radical initiator14.5% 13.3% 14.6% 14.5% 14.5% 14.5% 14.6% Nonreactive diluent 38.5%39.0% 36.9% 35.6% 35.6% 35.6% 35.9% Filler 41.9% 42.9% 43.7% 45.3% 45.3%45.3% 45.5% Miscellaneous^(a) 5.1% 4.8% 4.8% 4.6% 4.6% 4.6% 4.0% BondStrength After Cure (MPa) Cure at 23° C., Test at 82° C. 15.36 15.1413.45 14.56 12.84 12.38 10.65 Cure at 23° C., Test at 23° C. 22.28 20.7718.98 21.49 21.55 21.07 20.35 Cure at −10° C., Test at 23° C. 21.2820.42 18.97 19.80 19.49 18.30 16.32 Cure at −10° C., Test at −10° C.22.10 21.73 NE^(b) 21.65 NE^(b) NE^(b) NE^(b) Low Temperature vs.Standard Temperature Degree of Cure^(c) 95.5% 98.3% 99.9% 92.1% 90.5%86.9% 80.2% Phthalates present? No No No Yes Yes Yes Yes Notes to Table3 ^(a)Selected from amoung pigments;thixotropes;dyes and colorants; etc.^(b)NE - Not Evaluated ^(c)This value, calculated for the entries in thetable from their bond strengths, is the ratio of teh strength at 23° C.after cure at −10° C. compared to the strength at 23° C. after cure at23° C. expressed in percent.

A number of different formulations were tried and evaluated for strengthand performance characteristics after curing at different temperatures.In one series of experiments, adhesive formulations with differentratios/levels of AAEM and silane were prepared and evaluated. Thedifferent combinations that were tested include (expressed in terms ofweight % composition): a) 1.67% AAEM with 0.5% silane; b) 1.67% AAEMwith 1.5% silane; c) 5% AAEM with 1.67% silane and d) 5% AAEM with 1.5%silane). All of the foregoing formulations gave equivalent bondstrengths when cured at −10° C. and tested at 23° C.

As a result of the foregoing work and in accordance with one aspect ofthe present invention, a first component of the low-temperature curablereaction mixtures comprises 30-70% of a mixture comprising at least onereactive resin, at least one acetoacetoxy monomer, and at least onesilane monomer, with the balance selected from at least one of:accelerators, diluent monomers, inhibitors, dyes, fillers, pigments, andthixotropic agents; as well as combinations of the foregoing. A secondcomponent of the low-temperature curable reaction mixtures comprises10-25% of a free radical initiator with the balance selected from atleast one of: non-reactive diluents, dyes, fillers, pigments, andthixotropic agents, as well as combinations of the foregoing.

Additionally, according to another aspect of the present invention andas a result of the foregoing work, a first component of thelow-temperature curable reaction mixtures comprises 30-70% of aphthalate-free mixture comprising at least one reactive resin, at leastone acetoacetoxy monomer, and at least one silane monomer, with thebalance selected from at least one of: accelerators, diluent monomers,inhibitors, dyes, fillers, pigments, and thixotropic agents; as well ascombinations of the foregoing. A second component of the low-temperaturecurable reaction mixtures comprises 10-25% of a phthalate-free mixturecomprising of at least one free radical initiator with the balanceselected from at least one of: non-reactive diluents, dyes, fillers,pigments, and thixotropic agents, as well as combinations of theforegoing.

In a preferred aspect of the invention, the first component of theinventive adhesive composition comprises 4 mole ethoxylated bisphenol Adimethacrylate, 2-(acetoacetoxy)ethyl methacrylate, methacryloxypropyltrimethoxysilane; and at least one diluent monomer, and the secondcomponent comprises dibenzoyl peroxide. According to another aspect, afirst component of the inventive adhesive compositions additionallycomprises the reactive diluent monomers tetrahydrofurfuryl methacrylateand trimethylolpropane trimethacrylate. According to yet another aspectof the invention, the second component comprises a phthalate-freedibenzoyl peroxide composition.

Delivery Method

Many methods of delivery for adhesive compositions may be contemplated.For instance, adhesive components may be stored in relatively smallamounts in multi-chambered cartridges from which components aredispensed simultaneously. Mixing may take place manually or through astatic mixing nozzle. Alternately, the components may be storedseparately in large containers and mixed with mechanical dispensers justprior to use. Often, the selection of reactive resin and any diluentmonomers may need to reflect the delivery method or tool that will beused to introduce the adhesive into a substrate. Dispensing with manualtools presents challenges, especially for low temperature cureadhesives. It is therefore desirable that the viscosities of suchadhesive formulations can be adjusted in order to enable the end user toeasily install the adhesive under low temperature conditions. Ingeneral, low viscosity reactive resins are preferred for suchapplications. However, low viscosity can also be achieved through acombination of choice of reactive resin, choice and amount of diluentmonomer, and amount of filler. Accordingly, and as will be understood bythose skilled in the relevant art, the ingredients of the presentinvention may be formulated over a wide range in order to meet a varietyof viscosity criteria from water-thin to thick paste.

Without limiting the scope of the present invention, in one aspect adelivery method for the inventive adhesive compositions comprises usinga dual chamber cartridge to dispense the composition through a staticmixing nozzle using a dispensing tool. The dispensing tool can be of anypower configuration including, but not limited to manual, electric,battery operated or pneumatic. In one aspect of the present invention,the first and second components are each prepared separately and thencombined by mixing their ingredients in a large mechanical mixer. In oneembodiment, the components are placed in separated multi-component,side-by-side or coaxial adhesive cartridges for use in the field wherethey are dispensed through a static mixing nozzle using a dispensingtool.

An alternate delivery method for an adhesive composition preparedaccording to the present invention may involve delivering the twoseparate components in the field using dual tank bulk dispensingequipment. Yet another delivery method for an adhesive compositionaccording to the present invention would involve the use of frangiblecapsules. Thus a first, sealed capsule containing a first component ofthe inventive formulations may be situated inside a second, largercapsule. The second capsule also contains the second component of theformulation and is also sealed. In the field, such a dual capsule wouldbe placed into a bore hole and broken by either driving an anchorelement through the dual capsule or spinning the anchor element into thedual capsule. In such a frangible capsule delivery system, the dualcapsules become part of the adhesive and serve as a filler. Regardlessof the delivery technique employed, according to one aspect of thepresent invention, the first and second components are mixed in amountssuch that the weight ratio of the first component to the secondcomponent is approximately ten to one. In another aspect of the presentinvention, the first component makes up approximately 91% of the totalcomposition and the second component makes up approximately 9% of thetotal composition.

In one aspect, the formulations of the present invention improve uponadhesives of the prior art by providing an adhesive formulation that hashigh internal mechanical strength, high bond strength with the base andthe anchor, absorbs little water, has low toxicity, a viscosityappropriate for filling bore holes, and at the same is suitable forcuring at low temperatures. In another aspect, the formulations of thepresent invention, when applied and cured at low temperature, exhibitstrength and durability characteristics at both room temperatures andelevated temperatures that are at least equivalent to adhesives that arecurrently commercially available. That is, equivalent strength anddurability characteristics of the instant formulations can be realizedboth at room temperatures and elevated temperatures as compared tocommercially available adhesives, without the need for formulatingcompositions differently for use at different temperatures. Moreover,the inventive adhesive compositions provide the added advantage thatthey are phthalate free.

The present invention has been described above in detail with referenceto specific embodiments, Tables and Examples. These specific embodimentsshould not be construed as narrowing the scope of the invention, butrather as illustrative examples. Although preferred embodiments of theinvention are specifically disclosed and described above, it is to beunderstood that various modifications and substitutions are anticipatedand and may be made to the described compositions, as well as tomaterials, methods of manufacture and use, without departing from thebroad spirit or scope of the invention contemplated herein. Theinvention is further illustrated and described in the claims, whichfollow.

What is claimed:
 1. A method for manufacturing an adhesive composition,comprising: a. presenting a first portion, the first portioncomprising: 1) at least one reactive resin comprising a functionalmonomer; 2) at least one acetoacetoxy functional monomer; 3) at leastone silane monomer; and 4) at least one accelerant; b. presenting aseparately arranged second portion, the second portion comprising: 5) afree radical initiator; and c. combining the first portion with thesecond portion; wherein the free radical initiator is dibenzoyl peroxideand the accelerant is selected from the group consisting of:N,N-diisopropanol-p-toluidine; N,N-dihydroxyethyl-p-toluidine;N,N-methylhydroxyethyl-p-toluidine; and mixtures thereof.
 2. The methodof claim 1, wherein the reactive resin is selected from the groupconsisting of an acrylate monomer, an allylic resin, a bismaleimideresin, an epoxy acrylate resin, an epoxy methacrylate resin, amethacrylate monomer, a phenolic-based acrylate, a phenolic-basedmethacrylate, an unsaturated polyester resin, a urethane acrylate resin,a urethane methacrylate resin, a vinyl ester resin, and combinations ofany of the foregoing.
 3. The method of claim 1, wherein the acetoacetoxyfunctional monomer is selected from the group consisting of anacetoacetoxyethyl acrylate, an acetoacetoxyethyl methacrylate, adiacetone acrylamide, an acetoacetoxy vinyl ether, and combinations ofany of the foregoing.
 4. The method of claim 1, wherein the silanemonomer is selected from the group consisting of a methacryloxypropyltrimethoxysilane, a methacryloxypropylmethyl dimethoxy silane, amethacryloxypropyl triethoxy silane, an acryloxypropyl trimethoxysilane, an acryloxypropylmethyl dimethoxy silane, an acryloxypropyltriethoxy silane, a vinyl trimethoxysilane, a vinylmethyl dimethoxysilane, a vinyl triethoxy silane, and combinations of any of theforegoing.
 5. The method of claim 1, wherein the first portion furthercomprises: 6) at least one reactive diluent monomer selected form thegroup consisting of a monofunctional monomer, a multifunctional monomer,and combinations of the foregoing, wherein i) the monofunctional monomeris selected from the group consisting of methyl methacrylate, isopropylmethacrylate, isobutyl methacrylate, tert-butyl methacrylate, sterylmethacrylate, 2-phenoxyethyl methacrylate, tetrahydrofurfurylmethacrylate, glycidyl methacrylate, isobornyl methacrylate,hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutylmethacrylate, benzyl methacrylate, dicyclopentyl methacrylate,tert-butyl acrylate, steryl acrylate, 2-phenoxyethyl acrylate,tetrahydrofurfuryl acrylate, isobornyl acrylate, hydroxybutylmethacrylate, benzyl acrylate, dicyclopentyl acrylate, styrene, vinyltoluene, methyl styrene, allyl glycidyl ether, acrylamide,methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, andcombinations of any of the foregoing; and ii) the multifunctionalmonomer is selected from the group consisting of divinyl benzene, allylmethacrylate, allyl cinnimate, ethylene glycol dimethacrylate,diethlyene glycol dimethacrylate, triethylene glycol dimethacrylate,dipropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, cyclohexane dimethanol dimethacrylate,dicyclopentyl dimethacrylate, glyceryl trimethacrylate,trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate,ethylene glycol diacrylate, diethlyene glycol diacrylate, triethyleneglycol diacrylate, dipropylene glycol diacrylate, 1,3-butylene glycoldiacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate,dicyclopentyl diacrylate, glyceryl triacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol pentaacrylate, tris(2-hydroxy ethyl)isocyanuratetriacrylate, alkoxylated versions of any of the foregoing, metallicacrylates and methacrylates of zinc, magnesium and calcium, andcombinations of any of the foregoing.
 6. The method of claim 1, whereinthe polymerizable monomer is an ethoxylated bisphenol A dimethacrylate.7. The method of claim 1, wherein the acetoacetoxy functional monomer isacetoacetoxyethyl methacrylate.
 8. The method of claim 1, wherein thesilane monomer is methacyloxypropyl trimethoxysilane.
 9. The method ofclaim 1, wherein the dibenzoyl peroxide is phthalate free.
 10. Themethod of claim 1, wherein the wherein the polymerizable monomer is anethoxylated bisphenol A dimethacrylate, the acetoacetoxy functionalmonomer is acetoacetoxyethyl methacrylate, the silane monomer ismethacryloxypropyl trimethoxysilane, the accelerant is selected from thegroup consisting of N,N-diisopropanol-p-toluidine,N,N-dihydroxyethyl-p-toluidine, N,N-methylhydroxyethyl-p-toluidine, andcombinations thereof, and the dibenzoyl peroxide is phthalate free. 11.A method for anchoring an element in a structural body, comprising: a.providing a first portion, the first portion comprising: 1) anethoxylated bisphenol A dimethacrylate; 2) acetoacetoxyethylmethacrylate; 3) methacryloxypropyl trimethoxysilane; and 4) anaccelerant selected from the group consisting ofN,N-diisopropanol-p-toluidine, N,N-dihydroxyethyl-p-toluidine,N,N-methylhydroxyethyl-p-toluidine, and combinations thereof; b.providing a separately arranged second portion, the second portioncomprising: 5) phthalate free dibenzoyl peroxide; c. combining the firstportion with the second portion forming an adhesive composition; and d.anchoring said element in said structural body using said adhesivecomposition.
 12. The method of claim 11, wherein the element is selectedfrom the group comprising a metallic object, a steel rod, a steel bolt,a ceramic member, a concrete member, a masonry member, a plastic member,a glass member, a wood member, and combinations thereof.
 13. The methodof claim 11, wherein the structural body is selected from the groupcomprising concrete, masonry and combinations thereof.
 14. The method ofclaim 11, the first portion further comprising: 6) at least one reactivediluent monomer selected form the group consisting of a monofunctionalmonomer, a multifunctional monomer, and combinations of the foregoing,wherein i) the monofunctional monomer is selected from the groupconsisting of methyl methacrylate, isopropyl methacrylate, isobutylmethacrylate, tert-butyl methacrylate, steryl methacrylate,2-phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidylmethacrylate, isobornyl methacrylate, hydroxyethyl methacrylate,hydroxypropyl methacrylate, hydroxybutyl methacrylate, benzylmethacrylate, dicyclopentyl methacrylate, tert-butyl acrylate, sterylacrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate,isobornyl acrylate, hydroxybutyl methacrylate, benzyl acrylate,dicyclopentyl acrylate, styrene, vinyl toluene, methyl styrene, allylglycidyl ether, acrylamide, methacrylamide, N-methylol acrylamide,N-methylol methacrylamide, and combinations of any of the foregoing; andii) the multifunctional monomer is selected from the group consisting ofdivinyl benzene, allyl methacrylate, allyl cinnimate, ethylene glycoldimethacrylate, diethlyene glycol dimethacrylate, triethylene glycoldimethacrylate, dipropylene glycol dimethacrylate, 1,3-butylene glycoldimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate, neopentyl glycol dimethacrylate, cyclohexane dimethanoldimethacrylate, dicyclopentyl dimethacrylate, glyceryl trimethacrylate,trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate,ethylene glycol diacrylate, diethlyene glycol diacrylate, triethyleneglycol diacrylate, dipropylene glycol diacrylate, 1,3-butylene glycoldiacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate,dicyclopentyl diacrylate, glyceryl triacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol pentaacrylate, tris(2-hydroxy ethyl)isocyanuratetriacrylate, alkoxylated versions of any of the foregoing, metallicacrylates and methacrylates of zinc, magnesium and calcium, andcombinations of any of the foregoing.
 15. The method of claim 11,wherein the first portion and second portion are combined through astatic mixing nozzle.
 16. The method of claim 11, wherein the amount ofthe first portion is in the range of about 30% to about 70%.
 17. Themethod of claim 11, wherein the amount of the second portion is in therange of about 10% to 25%.
 18. The method of claim 11, wherein the ratioof the first portion to the second portion is about 10:1 (% weight). 19.A method for anchoring an element in a structural body, comprising: a.providing a first portion, the first portion comprising: 1) anethoxylated bisphenol A dimethacrylate; 2) acetoacetoxyethylmethacrylate; 3) methacryloxypropyl trimethoxysilane; and 4)phthalate-free dibenzoyl peroxide; and b. providing a separatelyarranged second portion, the second portion comprising: 5)N,N-diisopropanol-p-toluidine; c. combining the first portion with thesecond portion producing an adhesive composition; and d. anchoring theelement in the structural body using the adhesive composition.
 20. A kitfor an adhesive composition, comprising: a. a first portion having: 1)at least one reactive resin comprising a functional monomer; 2) at leastone acetoacetoxy functional monomer; 3) at least one silane monomer; and4) at least one accelerant selected from the group consisting ofN,N-diisopropanol-p-toluidine, N,N-dihydroxyethyl-p-toluidine,N,N-methylhydroxyethyl-p-toluidine, and combinations thereof; b. aseparately-maintained second portion comprising: 5) dibenzoyl peroxide;and c. instructions for use.
 21. The kit of claim 20, the first portionfurther comprising: 6) at least one reactive diluent monomer selectedform the group consisting of a monofunctional monomer, a multifunctionalmonomer, and combinations of the foregoing, wherein i) themonofunctional monomer is selected from the group consisting of methylmethacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butylmethacrylate, steryl methacrylate, 2-phenoxyethyl methacrylate,tetrahydrofurfuryl methacrylate, glycidyl methacrylate, isobornylmethacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate,hydroxybutyl methacrylate, benzyl methacrylate, dicyclopentylmethacrylate, tert-butyl acrylate, steryl acrylate, 2-phenoxyethylacrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, hydroxybutylmethacrylate, benzyl acrylate, dicyclopentyl acrylate, styrene, vinyltoluene, methyl styrene, allyl glycidyl ether, acrylamide,methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, andcombinations of any of the foregoing; and ii) the multifunctionalmonomer is selected from the group consisting of divinyl benzene, allylmethacrylate, allyl cinnimate, ethylene glycol dimethacrylate,diethlyene glycol dimethacrylate, triethylene glycol dimethacrylate,dipropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, cyclohexane dimethanol dimethacrylate,dicyclopentyl dimethacrylate, glyceryl trimethacrylate,trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate,ethylene glycol diacrylate, diethlyene glycol diacrylate, triethyleneglycol diacrylate, dipropylene glycol diacrylate, 1,3-butylene glycoldiacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate,neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate,dicyclopentyl diacrylate, glyceryl triacrylate, trimethylolpropanetriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol pentaacrylate, tris(2-hydroxy ethyl)isocyanuratetriacrylate, alkoxylated versions of any of the foregoing, metallicacrylates and methacrylates of zinc, magnesium and calcium, andcombinations of any of the foregoing.
 22. The kit of claim 20, whereinthe first portion is contained in a first chamber and the second portionis contained in a second chamber, both of the chambers configured in anarrangement selected from the group consisting of co-axial,side-by-side, bulk tank equipment, and combinations of any of theforegoing.
 23. The kit of claim 22, wherein at least one chamber isfrangible.
 24. The kit of claim 23, wherein the frangible chamber servesas a filler.
 25. The kit of claim 20, wherein the amount of the firstportion is in the range of about 30% to about 70%.
 26. The kit of claim20, wherein the amount of the second portion is in the range of about10% to 25%.
 27. The kit of claim 20, wherein the ratio of the firstportion to the second portion is about 10:1 (% weight).